[0001] The present invention relates to a coating composition, e.g. a dispersion or emulsion
and a method of preparing such composition. The invention also relates to the use
of the coating composition, for example for formation of paint films on substrates.
Background of the invention
[0002] It is commonly known in the art to use siccatives in coating dispersions such as
paint dispersions. Typically, such siccatives contain metal soaps (metallic driers).
Metal soaps may contain for example cobalt, lead, vanadium, or manganese but also
soaps with other metals are available in the art. A previously preferred metal soap
was cobalt soap due to its excellent performance with respect to drying time. Such
metallic driers also contribute to reduced tackiness. Also, such driers are dissolved
in suitable solvents, normally in aliphatic hydrocarbons which introduce up to 1 wt%
volatile organic compounds to a coating dispersion or emulsion. Such driers, however,
are hazardous to human health and may even be cancerogeneous.
[0003] The amount of drier used in waterborne systems is often used in higher concentrations
than in solventborne systems to compensate for losses of primary driers (or active
driers) such as cobalt, vanadium and manganese based driers.
[0004] While the solids portion of a coating dispersion adheres to the coated substrate,
the solvent component if solventborne evaporates and causes environmental concern.
The solvent materials are mostly volatile organic compounds (VOCS) that contribute
to the creation of ozone (smog) in the lower atmosphere and are toxic to human health.
Some solvents may also be classified as hazardous air pollutants (HAPs).
[0005] Alkyds are known to be used in coatings, in particular in paints. Such paints may
be applied by means of solventborne and waterborne formulations. However, in particular
waterborne paints may suffer from disadvantages such as low drying speed, drier incompatibility,
through-drying, surface defects, poor hardness etc.
[0006] The present invention intends to provide an environmentally adapted coating composition
which considerably reduces the metallic drier (active drier) content therein, or even
completely omits the presence thereof in order to minimize evaporation of volatile
organic compounds as a coating composition is drying on a substrate and hazardous
metals, in particular cobalt, remaining in the formed coating. A further objective
of the invention is to provide reduced yellowing of coatings.
[0007] The invention also intends to provide a composition which improves the vapour permeability
of the film formed from e.g. a coating dispersion. A further objective is to reduce
the drying time subsequent to application of such coating composition to a substrate.
A further objective is to provide a reduced tack-free time. Another objective is to
provide an improved dirt-pick up resistance to the film formed from the coating composition.
A further objective of the invention is to improve the block resistance of the composition.
A further objective is to provide an acceptable hardness to the coating. A further
important objective of the present invention is to provide a stable coating composition
which is not liable to gelling or precipitation. It is thus a requirement that the
coating composition can be stored for a certain period of time, for example at least
one year or at [east two years without detrimental effects caused by separation or
gelling. According to one embodiment, yet an objective is to provide an environmentally
adapted system which is waterborne. According to yet one embodiment, the invention
also intends to provide a composition having an improved hiding power.
[0008] The present invention intends to solve the problems referred to above.
The invention
[0009] The present invention relates to a coating composition comprising
- a) silanized colloidal silica particles having an average particle diameter ranging
from 2 to 150 nm and a weight ratio of silane to silica ranging from 0.05 to 0.4
- b) an alkyd-containing binder
- c) a carrier fluid selected from water and/or an organic solvent,
wherein the cobalt content of a cobalt based drier in the composition is less than
200 ppm based on the weight of the alkyd-containing binder or total weight of binder.
[0010] The carrier fluid is water and/or an organic solvent, preferably water. The coating
composition may thus be waterborne, solvent borne, a solution or a mixture thereof.
According to one embodiment, the carrier fluid is present in the composition, which
preferably is an aqueous dispersion, for example before drying is initiated thereof,
in an amount from about 20 to about 80, for example from about 30 to about 70, or
from about 40 to about 60 wt%.
[0011] According to one embodiment, the coating composition is a coating dispersion. In
the present application, when addressing a "coating composition" herein, both coating
dispersions, coating emulsions and coating solutions are comprised. For reasons of
simplicity, embodiments herein are often described as dispersions but may be applicable
also for any other composition, such as emulsions or solutions.
[0012] Preferably, the coating composition is stable. By the term "stable" is meant the
composition is present in an aqueous dispersion comprising components a)-c) wherein
no gelling or precipitation occurs at storage at a temperature from 15 to 30°C during
two months, preferably during four months, or most preferably during six months.
[0013] According to one embodiment, the coating composition is essentially free from active
driers. By "active driers" is meant driers which promote oxygen uptake, peroxide formation,
and peroxide decomposition at ambient temperatures, i.e. at a temperature from 0 to
40°. Preferably, the coating composition is free from active driers based on cobalt,
manganese, iron, cerium, vanadium, and/or lead. According to one embodiment, the metal
content of the active drier is present in the composition in an amount less than 200,
for example less than 20 or less than 2 ppm or 0 ppm based on the weight of alkyd-containing
binder or total weight of binder. According to one embodiment, the active drier, based
on cobalt, manganese, iron, cerium, vanadium, and/or lead, is present in the coating
composition in an amount less than 100, for example less than 10 or less than 1 ppm
or 0 ppm based on the weight of alkyd-containing binder or total weight of binder.
[0014] According to one embodiment, the coating composition is paint, enamel, lacquer or
varnish dispersion. Preferably, the composition is an aqueous dispersion or emulsion.
According to one embodiment, no active drier is present in the coating composition.
[0015] According to one embodiment, the coating composition comprises an auxiliary drier.
An auxiliary drier is not catalytically active at ambient temperatures, i.e. at a
temperature ranging from 0 to 40°C but may be able to enhance the activity of active
driers. According to one embodiment, auxiliary driers are based on metals selected
from barium, zirconium, calcium, bismuth, zinc, potassium, strontium, and/or lithium,
preferably zirconium.
[0016] According to one embodiment, the metal content of the auxiliary drier is present
in the composition in an amount less than 1%, for example less than 0.5% or less than
3000 ppm or 0.25 or 0 ppm based on the weight of alkyd-containing binder or total
weight of binder. According to one embodiment, the auxiliary drier based on barium,
zirconium, calcium, bismuth, zinc, potassium, strontium, and/or lithium is present
in the coating composition in an amount less than 10% , for example less than 5% or
less than 3 % or 0.25 or 0 ppm based on the weight of alkyd-containing binder or total
weight of binder. According to one embodiment, the composition comprises besides alkyd-containing
binder optionally any further binder. According to one embodiment, the weight ratio
of alkyd-containing binder to other binder ranges from about 2:1 to about 100:1, for
example from about 5:1 to about 100:1, such as 10:1 to about 100:1, or 50:1 to about
100:1.
[0017] According to one embodiment, alkyd-containing binder is present in the composition
in an amount from about 10 to about 90 wt%, for example from about 70 to about 90
wt%, or for example from about 10 to about 30 wt% based on the dry or carrier fluid
free weight of the composition.
[0018] According to one embodiment, the silanized colloidal silica particles are present
in the coating composition in an amount ranging from about 1 to about 50, preferably
from about 2 to about 25, more preferably from about 5 to about 20, or most preferably
from about 8 to about 15 wt% based on the dry or carrier fluid free weight of the
composition.
[0019] According to one embodiment, the weight ratio of silanized colloidal silica particles
to alkyd-containing binder or total amount of binder is in the range from about 0.05
to about 2, for example from about 0.1 to about 1, preferably from about 0.2 to about
0.6, more preferably from about 0.3 to about 0.5. This weight ratio can thus be based
on both alkyd-containing binder and total amount of binder present in the composition.
[0020] According to one embodiment, other binders than alkyd-containing or alkyd-based binders
may be comprised in the composition, for example acrylate-based binders, or epoxy-based,
or polyurethane-based binders, or combinations thereof. According to one embodiment,
the alkyd-containing binder is selected from tall oil-based, linseed oil-based, or
castor oil-based alkyds.
[0021] According to one embodiment, the carrier fluid is a component in the coating composition
before use of the coating composition, for example before application thereof on a
substrate, but is withdrawn, for example evaporated afterwards to allow the solid
materials to immobilize and form a coating, e.g. a thin protective film.
[0022] According to one embodiment, alkyds include waterborne and/or solventborne alkyd
coatings, such as waterborne and/or solventborne alkyd paints. According to one embodiment,
such coating compositions may be oxidatively drying. According to one embodiment,
alkyd coatings can be alkyd emulsions or colloidally dispersed alkyd resins. According
to one embodiment, waterborne alkyds are used. According to one embodiment, the alkyds
are modified, non-modified, or a mixture thereof. Alkyds can be prepared by condensation
polymerization of for example polyols, polybasic acids and/or fatty acids or triglyceride
oils.
[0023] According to one embodiment, an alkyd is a polyester modified by the addition of
fatty acids and other components. They are derived from polyols and a dicarboxylic
acid or carboxylic acid anhydride. There are two types of alkyd resins, drying (including
semi-drying) and non-drying alkyd resins. Both types are typically produced from dicarboxylic
acids or anhydrides, such as phthalic anhydride or maleic anhydride, and polyols,
such as trimethylolpropane, glycerine, or pentaerythritol.
[0024] Drying resins, triglycerides derived from polyunsaturated fatty acids are often derived
from plant and vegetable oils, e.g. linseed oil. These drying alkyds are cured in
air. The drying speed and the nature of the coatings depends on the amount and type
of drying oil employed (more polyunsaturated oil means faster reaction in air) and
use of metal salts, the so-called oil drying agents. These metal complexes catalyze
crosslinking of the unsaturated sites.
[0025] According to one embodiment, alkyd coatings are produced in two processes; the fatty
acid process and the alcoholysis or mono-glyceride process. Higher quality alkyds
are produced in the fatty acid process where the composition of the resulting resin
can be more precisely controlled. In this process an acid anhydride, a polyol and
an unsaturated fatty acid are combined and cooked together until the product has achieved
a predetermined level of viscosity. For example penta alkyds are made this way. More
economical alkyd resins are produced from the alcoholysis or glyceride process where
end product quality control is not as paramount. In this process raw vegetable oil,
high in unsaturated component, is combined with additional polyol and heated to cause
transesterification of the triglycerides into a mixture of mono- and diglyceride oils.
To this resulting mixture, acid anhydride is added to build up the molecular weight
of the resin into roughly the same product as in the fatty acid process. However,
the alcoholysis process produces a more randomly oriented structure. To remove the
water produced as a by-product and to increase the reaction rate, surplus phthalic
anhydride was added. Water is thus removed with the unreacted acid by heating the
bulk to a temperature needed to do this. Also, xylene can be added to produce an azeotrope
with the water resulting in greater control at a lower temperature resulting in resins
at a lower viscosity which are useful in making high solids paints (known as the AZO
process). In both cases the resulting product is a polyester resin to which pendant
drying oil groups are attached.
[0026] Alkyd coatings may be classified in three classes; long, medium, and short. These
terms represent the relative fraction of the drying oil component in the resin. Long
oil alkyds have a high percentage of drying oil content and are generally sold as
medium duty coatings for the consumer market. Medium oil alkyds have less drying oil
and have a higher percentage of large molecular weight polyester backbone. They dry
slower and are employed as high gloss coatings and wood finishes. At the bottom end
are short oil alkyds where the percentage of drying oil is very low in relation to
the base polyester polymer or backbone chain. These coatings will not air dry or harden
unless heated. Short oil alkyds are employed as baking enamels for finished metal
products, in conjunction with amino/formaldehyde resins. Alkyds are also modified
with phenolic resin, styrene, vinyl toluene, acrylic monomers (to make them dry more
quickly) and polyurethanes. By adding certain modifying resins, it is possible to
produce thixotropic alkyds for decorative use. The latest alkyds are short oil A/D
resins where the oil length is shortened by chain stopping with benzoic acid and now
para tertiary butyl benzoic acid (Alkydal M 48). Alkyds for decorative use have extra
oil cooked in to lengthen them and to make them more durable. Short oil resins used
in stoving enamels are made from non-drying saturated oils or fatty acids. These usually
have much higher hydroxyl and acid values, to be able to react with the hydroxyl groups
of the amino resins. These mixtures are usually stabilized with amines to prevent
gelling on storage.
[0027] Typical sources of drying oils for alkyd coatings are, linseed oil, tung oil, sunflower
oil, safflower oil, walnut oil, soybean oil, fish oil, corn oil, D.C.O. (made by dehydrating
Castor oil, which creates a semi drying, conjugated, oil/fatty acid) and tall oil
(resinous oil by-product from pulp and paper manufacturing). Non-drying/ plasticizer
resins are made from castor, palm, coconut oils and Cardura (a synthetic fatty, Versatic
acid ex Shell). Suitable alkyds are further disclosed in e.g.
Alkyd Resins, p.1-18, Jones, N. Frank, Coatings Research Institute, Eastern Michigan
University, Ypsilanti, MI 48197, USA, 2005, Wiley-VCH Verlag GmbH & Co.KgaA, Weinheim
10.1002/14356007.a01_409.
[0029] The silanized colloidal silica particles may have a specific surface area from about
20 to about 1500, specifically from about 50 to about 900, and more specifically from
about about 70 to about 600, or from about 120 to about 600, or from about 200 to
about 400, or from about 220 to about 360 m
2/g as measured by the BET method.
[0030] The silanized colloidal silica particles, for example as disclosed in
EP 2087045 have an average particle diameter ranging from 2 to 150 nm, for example from about
3 to about 60 such as from about 5 to about 40 or from about 5 to about 25 nm, or
from about 6 to about 12, or from about 7 to about 10 nm.
[0031] The colloidal silica particles may have a narrow particle size distribution, i.e.
a low relative standard deviation of the particle size. The relative standard deviation
of the particle size distribution is the ratio of the standard deviation of the particle
size distribution to the mean particle size by numbers. The relative standard deviation
of the particle size distribution may be lower than about 60 % by numbers, specifically
lower than about 30 % by numbers, and more specifically lower than about 15 % by numbers.
[0032] The colloidal silica particles are dispersed in an aqueous medium, specifically in
the presence of stabilising cations such as K
+ Na
+, Li
+, NH
4+, organic cations, primary, secondary, tertiary, and quaternary amines, or mixtures
thereof so as to form an aqueous silica sol. The colloidal silica particles as such
used in the present invention do not gel and remain in colloidally dispersed form
for at least 2 months, preferably at least 4 months and most preferably at least 6
months. However, also dispersions comprising organic mediums, e.g. acetone may be
used, specifically in an amount of from about 1 to about 20, specifically from about
1 to about 10, and more specifically from about 1 to about 5 volume percent of the
total medium volume. However, in one specific embodiment aqueous silica sols without
any further mediums are used. The colloidal silica particles may be negatively charged.
The silica content in the silica sol may be from about 10 to about 80, specifically
from about 20 to about 70, and more specifically from about 30 to about 60 wt%. The
higher the silica content, the more concentrated the resulting silanised colloidal
silica dispersion. The pH of the silica sol may be from about 1 to about 13, specifically
from about 6 to about 12, and more specifically from about 7.5 to about 11. However,
for aluminium-modified silica sols, the pH may be from about 1 to about 12, specifically
from about 3.5 to about 11. According to one embodiment, the colloidal silica particles
are dispersed in an organic medium, for example as described in
EP2010/066551.
[0033] The silica sol may have an S-value from about 20 to about 100, specifically from
about 30 to about 90, and more specifically from about 60 to about 90.
[0034] It has been found that dispersions with an S-value within these ranges can improve
the stability of the resulting dispersion. The S-value characterises the extent of
aggregation of colloidal silica particles, i.e. the degree of aggregate or microgel
formation. The S-value has been measured and calculated according to the formulas
given in
J. Phys. Chem. 60(1956), 955-957 by Iler, R.K. & Dalton, R.L.
[0035] The S-value depends on the silica content, the viscosity, and the density of the
colloidal silica particles. A high S-value indicates low microgel content. The S-value
represents the amount of SiO
2 in percent by weight present in the dispersed phase of e.g. a silica sol. The degree
of microgel can be controlled during the production process as further described in
e.g.
US 5368833.
[0036] The colloidal silica particles, also referred to as silica sols herein, can be produced
from different raw materials, for example from precipitated silica, micro silica (silica
fume), pyrogenic silica (fumed silica) or silica gels with sufficient purity, and
mixtures thereof after conventional processing thereof; they may be silanised by way
of the method described in
WO2004/035474. The silica sol may also, typically, be obtained from waterglass as disclosed in
e.g.
US,5,368,833 which may be obtained from sand, soda or other raw materials. TEOS (Tetraethyl orthosilicate)
may also be used as source for production of silica sol.
[0037] The colloidal silica particles can be modified with any suitable silane compound.
For example, tris-(trimethoxy)silane, octyl triethoxysilane, methyl triethoxysilane,
methyl trimethoxysilane; bis-(3-[triethoxysilyl]propyl)polysulfide, beta-(3,4-epoxycyclohexyl)-ethyl
trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl
triisopropoxysilane, gamma-methacryloxypropyl triethoxysilane, octyltrimethyloxy silane,
ethyltrimethoxy silane, propyltriethoxy silane, phenyltrimethoxy silane, cyclohexyltrimethoxy
silane, cyclohexyltriethoxy silane, dimethyldimethyoxy silane, 3-chloropropyltriethoxy
silane, 3-methacryloxypropyltrimethoxy silane, i-butyltriethoxy silane, trimethylethoxy
silane, phenyldimethylethoxy silane; silanes containing an epoxy group (epoxy silane),
preferably glycidoxy and/or a glycidoxypropyl group such as gamma-glycidoxypropyl
trimethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, (3-glycidoxypropyl)triethoxy
silane, (3-glycidoxypropyl) hexyltrimethoxy silane, beta-(3,4-epoxycyclohexyl)-ethyltriethoxysilane;
silanes containing a vinyl group such as vinyl triethoxysilane, vinyl trimethoxysilane,
vinyl tris-(2-methoxyethoxy)silane, vinyl methyldimethoxysilane, vinyl triisopropoxysilane;
hexamethyldisiloxane, trimethylsilyl chloride, vinyltriethoxy silane, hexamethyldisilizane,
and mixtures thereof. According to one embodiment, silane compounds with mercapto
functionality may be used, for example 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy
silane, HS(CH
2)
3, Si(OCH
3)
3, mercaptosilane possessing at least one hydroxyalkoxysilyl group and/or a cyclic
dialkoxysilyl group, gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane,
gamma-mercaptopropyl trimethoxysilane.
[0038] According to one embodiment, silane compounds with amido-functionality, for example
(meth)acryl amide groups; ureido-functionality, amino-functionality, ester functionality
and/or isocyanato functionality such as tris-[3-(trimethoxysilyl)propyl]isocyanurate
may be used. Suitable ureido functional silanes include β-ureidoethyl-trimethoxysilane,
β-ureidoethyl-triethoxysilane, γ-ureidoethyltrimethoxysilane, and/or γ-ureidopropyl-triethoxysilane.
Silane compounds with ureido functionality may have the structure B
(4-n)-Si-(A-N(H)-C(O)-NH
2)
n, wherein A is an alkylene group containing from 1 to about 8 carbon atoms, B is a
hydroxyl or alkoxy group containing from 1 to about 8 carbon atoms, and n is an integer
from 1 to 3 provided that if n is 1 or 2, each B may be the same or different.
[0039] Preferably, an epoxy group-containing silane is used, most preferably glycidoxy and/or
a glycidoxypropyl group such as gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl
methyldiethoxysilane, (3-glycidoxypropyl)triethoxy silane
[0040] According to one embodiment, silane with amino-functionality can be for example aminomethyltriethoxysilane,
N-(β-aminoethyl)aminomethyltrimethoxysilane, aminomethylmethyl diethoxysilane, N-(β-aminoethyl)methyltriethoxysilane,
γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminoisobutyltrimethoxysilane,
N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane.
Further examples of the above silane functionalities which may be used include those
mentioned in
US 5,928,790 and
US 4,927,749, hereby incorporated by reference.
[0041] According to one embodiment, the silane compound is monomeric. According to one embodiment,
the silane compound is oligomeric.
[0042] In order to prepare the silanised colloidal silica particles, silane compounds and
colloidal silica particles can be mixed continuously, for example in an aqueous phase,
for example at a temperature from about 20 to about 95, such as from about 50 to about
75, or from about 60 to about 70 °C. Silane is for example slowly added to the silica
particles under vigorous agitation at a temperature above about 60 °C and at a controlled
rate, which suitably is from about 0.01 to about 100, such as from about 0.1 to about
10, from about 0.5 to about 5, or from about 1 to about 2 silane molecules per nm
2 colloidal silica surface area (on the colloidal silica particles) and hour. The addition
of silane can be continued for any suitable time depending on the addition rate, amount
of silane to be added, and degree of desired silylation. However, the addition of
silane can be continued up to about 5 hours, or up to about 2 hours until a suitable
amount of silane compounds has been added. According to one embodiment, from about
0.1 to about 6, such as from about 0.3 to about 3, or from about 1 to about 2 silane
molecules per nm
2 surface area of the colloidal silica particles is added. Continuous addition of silane
to the colloidal particles may be particularly important when preparing highly concentrated
silanised silica dispersions having a silica content up to about 80 wt%.
[0043] According to one embodiment, silane can be diluted before mixing it with the colloidal
silica particles, e.g. with water to form a premix of silane and water, suitably in
a weight ratio of from about 1:8 to about 8:1, from about 3:1 to about 1:3, or from
about 1.5:1 to about 1:1.5. The resulting silane-water solution is substantially clear
and stable and easy to mix with the colloidal silica particles.
[0044] The weight ratio of silane to silica in the dispersion may be from 0.05 to 0.4, and
more specifically from about 0.1 to about 0.5, or from about 0.2 to about 0.4 or from
about 0.2 to about 0.3.
[0045] Further suitable embodiments of silane, colloidal silica and preparation of silanised
silica are disclosed in
EP 1554221 B1,
Preferably, the silanized colloidal silica particles can remain stably dispersed,
i.e. remain colloidally dispersed without gelling or precipitation at normal storage
at a temperature from 15 to 35 °C for a period of at least 2 months, preferably at
least 4 months, and most preferably for at least 6 months. Preferably, the composition
according to the claimed invention also can remain stable, i.e. without gelling or
precipitation at normal storage at a temperature from 15 to 35 °C for a period of
at least 2 months, preferably at least 4 months, and most preferably for at least
6 months, or most preferably 1 year.
[0046] Coating compositions may vary, with different types and amounts of pigments, binders,
additives, and carrier fluids. The differences in coating compositions provide film
characteristics specifically set for the part and its end-use. Often, one type of
coating cannot be formulated to provide all of the desired properties. Several layers
of different coating material may be applied to a surface to form a coating film that
will thoroughly protect the part. The first coat is typically called the primer, or
undercoat, and the final layers are called topcoats. Regardless of the coating formulation
or number of layers applied, proper preparation, application techniques, and curing
processes may be necessary for the desired coating characteristics to be achieved.
[0047] According to one embodiment, depending on the use of the coating, the coating composition
comprises several binders, for example two or three binders, in combination. According
to one embodiment, the coating composition comprises pigment particles which typically
are colorant portion of the coating composition, for example titanium oxide. The pigment
may also be used to provide corrosion protection, stability in ultraviolet (UV) light,
or protection from mold, mildew or bacteria. Others can be used for their conductive
ability, texture, or metallic or pearlescent appearance. According to one embodiment,
the coating composition comprises a filling agent, for example talcum and calcium
carbonate which can be used to lower the cost of a paint obtainable from the coating
(paint) dispersion. According to one embodiment, a filler and/or pigment is present
in the coating composition in an amount ranging from about 10 to about 80, for example
from about 20 to about 60, or from about 30 to about 50 wt% based on the total dry
or carrier fluid-free weight of the composition.
[0048] According to one embodiment, the coating composition comprises a thickener to regulate
the viscosity of the paint. According to one embodiment, a thickener is present in
the coating composition in an amount from about 0.1 to about 2 wt% based on the dry
weight or carrier fluid-free weight of the composition. According to one embodiment,
yet further additives may be present which are usually low molecular weight chemicals
in coating formulations that allow coatings to perform specific functions but do not
contribute to colouring. Non-pigment additives include stabilizers to block attacks
of ultraviolet light or heat, curing additives to speed up the crosslinking reaction,
co-solvents to increase viscosity, or plasticizers to improve uniform coating. According
to one embodiment, a stabilizer is present in the composition in an amount from about
0.1 to about 3 wt% based on the total dry or carrier fluid-free weight of the composition.
According to one embodiment, a curing agent such as a UV initiator is present in the
coating composition in an amount ranging from about 0.1 to about 1 wt% based on the
total dry or solvent-free weight of the composition.
[0049] The invention also relates to a method of producing a coating composition comprising
mixing
- a) silanized colloidal silica particles having an average particle diameter ranging
from 2 to 150 nm and a weight ratio of silane to silica of 0.05 to 0.4; and
- b) an alkyd-containing binder; and
- c) a carrier fluid selected from water and/or an organic solvent,
wherein the metal content of a cobalt drier added to the composition is less than
200 ppm based on the weight of the alkyd-containing binder or total weight of binder
in the coating composition.
[0050] Preferably, amounts of components a-c mixed are as defined herein above so as to
result in desired proportions of the claimed composition as defined herein. Specifically,
the metal content of the cobalt-based drier or other active drier as defined herein
added to the composition is less than 200 ppm, for example less than 20 ppm or less
than 2 ppm based on the weight of the alkyd-containing binder or total weight of binder
of the forming composition. According to one embodiment, no active drier is added
to the coating composition. According to one embodiment, an auxiliary drier as defined
herein is added to the composition, preferably in amounts as described herein resulting
in an amount of less than 100, for example less than 10 or less than 1 ppm based on
the alkyd-containing binder or total weight of binder. According to one embodiment,
the silanized colloidal silica particles are added to the coating formulation in an
amount ranging from about 1 to about 50, for example from about 2 to about 25, for
example about 5 to about 20, or from about 8 to about 15 wt% based on the resulting
total dry or carrier fluid free weight of the composition. According to one embodiment,
silanized colloidal silica particles and alkyd-containing binder or total amount of
binder are added in a weight ratio of silanized silica to binder ranging from about
0.05 to about 2. According to one embodiment, the silica particles and the alkyd-containing
binder are mixed in an aqueous dispersion. According to one embodiment, the silica
particles and the alkyd- containing binder are mixed at a temperature ranging from
about 20 to about 90 °C, for example from about 20 to about 35 °C. The invention also
relates to a coating composition obtainable from the method as defined herein.
[0051] The invention also relates to the use of a coating composition for coating a substrate,
for example a wood, plastic substrate, cementitious substrate, brick substrate, ceramic
material, metallic substrate, mineral substrate or the like. Typically, the coating
composition is transformed to a surface coating of a substrate by drying at suitable
conditions, for example by simple solvent evaporation or air-drying at ambient or
slightly elevated temperatures.
[0052] The invention being thus described, it will be obvious that the same may be varied
in many ways. Such variations are not to be regarded as a departure from the gist
and scope of the present invention, and all such modifications as would be obvious
to one skilled in the art are intended to be included within the scope of the claims.
While the examples here below provide more specific details of the reactions, the
following general principles may here be disclosed. The following examples will further
illustrate how the described invention may be performed without limiting the scope
of it.
[0053] All parts and percentages refer to part and percent by weight, if not otherwise stated.
Examples
[0054] A formulation of components 1-6 was prepared by mixing the components in the prescribed
amounts to form a grinding paste which was milled during 20 minutes by means of a
Dispermat® CV equipped with a dissolver disc rotating at a radial velocity of 20 m/s.
Subsequently, components 7-11 were let down to the grinding paste in prescribed amounts
under gentle agitation by means of an agitator.
Table 1 - Paint formulation
| Products |
Weight parts |
| Grinding paste |
|
| 1. Water |
202.5 |
| 2. Coadis BR95 |
15 |
| 3. Coapur XS22 |
22.5 |
| 4. Byk 093 |
6 |
| 5. KRONOS® 2190 |
300 |
| 6. Omyacoat 850OG |
195 |
| Let down |
|
| 7. water |
72 |
| 8. Aquaflow nhs 350 |
30 |
| 9. Coapur XS22 |
15 |
| 10. Ser Ad FA 179 |
4.5 |
| 11. SYNAQUA 4804 |
592.5 |
| Total |
1458 |
[0055] Byk 093 is an antifoaming agent. Coadis BR95 is a dispersant for alkyd emulsion systems.
CoapurXS22 is a polyurethane thickener. Kronos is a titanium dioxide pigment. AquaflowTM
is a thickening additive for waterborne decorative coating applications. SER AD FA
179 is an antifoamant/wetting agent. Additol VXW 6206 (siccative) is a cobalt-containing
drying agent. SYNAQUA 4804 is a short oil alkyd emulsion. Omyacoat ® 850 OG designates
a calcium carbonate sold by the company OMYA ® which is a specific dispersant for
alkyd emulsion systems. Octa-Soligen Zirconium 10® aqua is a zirconium-containing
cobalt-free drying siccative.
Table 2 - Characteristics of the paint formulation
| Density (g/cm3) |
1.34 |
| Weight % Solids (%) |
56 |
| Volume % Solids (%) |
41 |
| PVC (%) |
33 |
| VOC (water incl.) (g/L) |
0 |
[0056] Silica products (Bindzil® CC301 and Bindzil® CC401, Bindzil® CC151, Bindzil® CC302)
were mixed with the paint formulation. Paint A reference was prepared by addition
of 1.5 wt% based on dry resin of Additol VXW 6206 (a cobalt-containing drying siccative)
to the formulation of table 1 (Paint A). Also, a reference without Bindzil and cobalt-containing
siccative was used (Paint B). In addition, paint C (reference) was prepared by addition
of a siccative agent: Octa-Soligen Zirconium 10 aqua (a zirconium-containing cobalt-free
drying siccative), 0.15 wt% Zr metal (equal to 1.5 wt% Octa-Soligen product), based
on dry resin (to the formulation of table 1 (Paint C). Also, the further compositions
from the paint formulation were prepared by addition of Bindzil CC products according
to the below:
Table 3: Coating formulations
| Paint A - REF: cobalt siccative agent + formulation of Table 1 |
| Paint B - REF contains formulation of table 1 (cobalt-free). |
| Paint B21 contains 95 g paint B + 5 g Bindzil CC301 |
| Paint B22 contains 90 g paint B + 10 g Bindzil CC301 |
| Paint B23 contains 85 g paint B + 15 g Bindzil CC301 |
| Paint B31 contains 95 g paint B + 5 g Bindzil CC401 |
| Paint B32 contains 90 g Paint B + 10 g Bindzil CC401 |
| Paint B33 contains 85 g Paint B + 15 g Bindzil CC401 |
| Paint B1 contains 90 g paint B + 10 g Bindzil CC151 |
| Paint B4 contains 90 g paint B + 10 g Bindzil CC302 |
| Paint C - REF: zirconium siccative agent (cobalt-free) + formulation of table 1 |
| Paint C21 contains 85 g paint C + 15 g Bindzil CC301 |
Dirt Pick-Up tests (DPU)
[0057] DPU tests were performed by applying the paints by means of a brush on a pine wood
substrate in two layers (24 hours between applications of the two layers). After 1
and 2 months of drying at room temperature, the surfaces were contaminated with either
a water-based solution with red iron oxide or water-based solution with carbon black
as set out below. The contamination was applied by means of spraying. The contaminated
systems were subsequently left to dry 24 hours at room temperature. The contaminated
surfaces were washed with water. The CIELAB colour system was used and the values
of L, a, b, and delta E were determined as described in
Applications Note, Insight on Color, Vol.8, 9 from Hunter Associates Laboratory (www.hunterlab.com/appnotes/an07-96a.pdf)
and Chromameter manual CR-200, p.71-75 www.konicaminolta.com/content/download/4728/34959/CR-200.PDF.
Dirtying solutions
| - Red iron oxide |
1 gram pigment + 200 ml water |
| - Carbon black (printex G) |
1 gram pigment + 200 ml water |
Table 4 - Red iron oxide contamination - alkyd paints - drying time 2 months
| |
INITIAL before contamination |
Surface washing with water |
|
| L |
a |
b |
L |
a |
b |
delta E |
| Paint A-REF |
94.78 |
-0.82 |
2.75 |
94.37 |
-0.2 |
3.04 |
|
| |
95.03 |
-0.66 |
3.11 |
94.28 |
0.03 |
3.3 |
|
| |
94.97 |
-0.72 |
2.65 |
94.52 |
-0.13 |
3.23 |
|
| |
94.92 |
-0.74 |
2.73 |
94.29 |
-0.09 |
3.22 |
|
| |
94.97 |
-0.59 |
2.84 |
94.21 |
-0.08 |
3.37 |
|
| Average |
94.93 |
-0.71 |
2.82 |
94.33 |
-0.09 |
3.23 |
0.95 |
| |
|
|
|
|
|
|
|
| Paint B-REF |
95.31 |
-0.54 |
1.88 |
90.49 |
5.01 |
7.33 |
|
| without Co |
95.54 |
-0.66 |
2.19 |
90.3 |
5.1 |
7.49 |
|
| |
95.14 |
-0.51 |
1.74 |
90.91 |
4.68 |
7.03 |
|
| |
95.06 |
-0.49 |
1.65 |
91.2 |
4.18 |
7.1 |
|
| |
95.49 |
-0.64 |
1.97 |
92.27 |
3.08 |
5.98 |
|
| Average |
95.31 |
-0.57 |
1.89 |
91.03 |
4.41 |
6.99 |
8.31 |
| |
L |
a |
b |
L |
a |
b |
delta E |
| B21 |
95.5 |
-0.55 |
1.94 |
92.14 |
3.37 |
5.9 |
|
| |
95.47 |
-0.54 |
1.89 |
92.79 |
2.42 |
5.42 |
|
| |
95.44 |
-0.57 |
1.96 |
92.84 |
2.62 |
5.37 |
|
| |
95.22 |
-0.46 |
1.66 |
93.31 |
1.98 |
4.96 |
|
| |
95.36 |
-0.57 |
1.74 |
93.56 |
1.73 |
4.93 |
|
| Average |
95.40 |
-0.54 |
1.84 |
92.93 |
2.42 |
5.32 |
5.19 |
| |
|
|
|
|
|
|
|
| B22 |
95.61 |
-0.5 |
1.74 |
94.14 |
1.05 |
3.53 |
|
| |
95.59 |
-0.5 |
1.88 |
93.17 |
2.58 |
4.8 |
|
| |
95.6 |
-0.5 |
1.9 |
94.44 |
0.74 |
3.2 |
|
| |
95.36 |
-0.47 |
1.54 |
94.61 |
0.44 |
2.92 |
|
| |
95.27 |
-0.44 |
1.57 |
94.25 |
0.95 |
3.31 |
|
| Average |
95.49 |
-0.48 |
1.73 |
94.12 |
1.15 |
3.55 |
2.80 |
| |
|
|
|
|
|
|
|
| B23 |
95.31 |
-0.47 |
1.49 |
94.72 |
0.57 |
2.78 |
|
| |
95.55 |
-0.49 |
1.6 |
94.35 |
0.82 |
3.2 |
|
| |
95 |
-0.51 |
1.08 |
94.86 |
0.37 |
2.86 |
|
| |
95.26 |
-0.43 |
1.46 |
94.74 |
0.34 |
2.75 |
|
| |
95.07 |
-0.38 |
1.32 |
95 |
0.19 |
2.54 |
|
| Average |
95.24 |
-0.46 |
1.39 |
94.73 |
0.46 |
2.83 |
1.78 |
| |
|
|
|
|
|
|
|
| B31 |
95.14 |
-0.49 |
1.6 |
92.62 |
2.6 |
5.74 |
|
| |
95.36 |
-0.56 |
1.9 |
93.74 |
1.15 |
4.45 |
|
| |
95.32 |
-0.54 |
1.67 |
93.7 |
1.28 |
4.37 |
|
| |
95.15 |
-0.45 |
1.63 |
93.78 |
1.12 |
4.09 |
|
| |
95.28 |
-0.57 |
1.63 |
93.42 |
1.36 |
4.42 |
|
| Average |
95.25 |
-0.52 |
1.69 |
93.45 |
1.50 |
4.61 |
3.99 |
| |
|
|
|
|
|
|
|
| B32 |
95.04 |
-0.31 |
1.74 |
93.34 |
1.69 |
4.62 |
|
| |
95.13 |
-0.42 |
1.83 |
93.1 |
1.66 |
4.39 |
|
| |
94.85 |
-0.41 |
1.57 |
94.01 |
0.76 |
3.5 |
|
| |
94.87 |
-0.29 |
1.55 |
94.31 |
0.32 |
2.8 |
|
| |
94.84 |
-0.29 |
1.52 |
94.02 |
0.92 |
3.73 |
|
| Average |
94.95 |
-0.34 |
1.64 |
93.76 |
1.07 |
3.81 |
2.85 |
| |
|
|
|
|
|
|
|
| B33 |
95.14 |
-0.32 |
1.94 |
94.24 |
0.55 |
2.99 |
|
| |
95.14 |
-0.38 |
1.88 |
94.01 |
0.77 |
3.23 |
|
| |
95.17 |
-0.33 |
1.92 |
94.18 |
0.69 |
3.27 |
|
| |
94.96 |
-0.33 |
1.75 |
94.47 |
0.33 |
2.93 |
|
| |
94.98 |
-0.37 |
1.74 |
94.24 |
0.32 |
2.65 |
|
| Average |
95.08 |
-0.35 |
1.85 |
94.23 |
0.53 |
3.01 |
1.69 |
Table 5 - Red iron oxide contamination - alkyd paints - drying time 1 month
| |
INITIAL before contamination |
Surface washing with water |
|
| L |
a |
b |
L |
a |
b |
delta E |
| Paint C-REF |
94.92 |
-0.44 |
1.7 |
90.6 |
4.58 |
5.58 |
|
| |
94.83 |
-0.41 |
1.68 |
90.92 |
4.13 |
5.55 |
|
| |
94.68 |
-0.39 |
1.41 |
91.26 |
3.8 |
5.13 |
|
| |
95.07 |
-0.54 |
1.73 |
90.09 |
4.83 |
5.66 |
|
| |
95.03 |
-0.41 |
1.71 |
90.15 |
5.03 |
6.25 |
|
| Average |
94.91 |
-0.44 |
1.65 |
90.60 |
4.47 |
5.63 |
7.65 |
| |
|
|
|
|
|
|
|
| Paint C21 |
94.58 |
-0.11 |
1.28 |
93.58 |
1.41 |
2.47 |
|
| |
94.54 |
-0.18 |
0.96 |
93.49 |
1.48 |
2.84 |
|
| |
94.72 |
-0.28 |
0.96 |
93.42 |
1.38 |
2.39 |
|
| |
94.77 |
-0.05 |
1.45 |
93.72 |
1.3 |
2.61 |
|
| |
94.89 |
-0.26 |
1.27 |
92.93 |
2.05 |
3.11 |
|
| Average |
94.70 |
-0.18 |
1.18 |
93.43 |
1.52 |
2.68 |
2.60 |
Table 6 - Carbon black contamination - alkyd paints - drying time 2 months
| |
INITIAL before contamination |
Surface washing with water |
| L |
A |
b |
L |
a |
b |
delta E |
| Paint A-REF |
95.06 |
-0.68 |
3.07 |
88.03 |
-0.27 |
3.01 |
|
| |
95.08 |
-0.74 |
3 |
86.05 |
-0.1 |
3.06 |
|
| |
94.89 |
-0.8 |
2.45 |
87.42 |
-0.09 |
3.19 |
|
| |
94.7 |
-0.71 |
2.27 |
89.74 |
-0.36 |
3.16 |
|
| |
94.98 |
-0.57 |
2.85 |
89.83 |
-0.54 |
2.94 |
|
| Average |
94.94 |
-0.70 |
2.73 |
88.21 |
-0.27 |
3.07 |
6.75 |
| |
|
|
|
|
|
|
|
| Paint B-REF |
95.33 |
-0.53 |
1.93 |
66.1 |
0.33 |
1.89 |
|
| |
95.41 |
-0.57 |
2.02 |
63.2 |
-0.03 |
2.2 |
|
| |
95.24 |
-0.56 |
1.9 |
65.32 |
-0.1 |
1.88 |
|
| |
95.11 |
-0.46 |
1.72 |
64.27 |
0.39 |
2.06 |
|
| |
95.27 |
-0.52 |
1.83 |
64.96 |
0.37 |
2.03 |
|
| Average |
95.27 |
-0.53 |
1.88 |
64.77 |
0.19 |
2.01 |
30.51 |
| |
|
|
|
|
|
|
|
| B21 B |
95.5 |
-0.55 |
1.94 |
71.55 |
-0.1 |
2.08 |
|
| |
95.47 |
-0.54 |
1.89 |
69.16 |
-0.16 |
2.17 |
|
| |
95.44 |
-0.57 |
1.96 |
73.68 |
-0.11 |
2.05 |
|
| |
95.22 |
-0.46 |
1.66 |
73.51 |
-0.03 |
2.11 |
|
| |
95.36 |
-0.57 |
1.74 |
72.24 |
-0.21 |
2.24 |
|
| Average |
95.40 |
-0.54 |
1.84 |
72.03 |
-0.12 |
2.13 |
23.38 |
| |
|
|
|
|
|
|
|
| B22 |
95.61 |
-0.5 |
1.74 |
78.44 |
-0.27 |
2 |
|
| |
95.59 |
-0.5 |
1.88 |
76.25 |
-0.1 |
2.16 |
|
| |
95.6 |
-0.5 |
1.9 |
83.84 |
-0.52 |
2.05 |
|
| |
95.36 |
-0.47 |
1.54 |
79.96 |
-0.33 |
2.2 |
|
| |
95.27 |
-0.44 |
1.57 |
80.35 |
-0.31 |
1.93 |
|
| Average |
95.49 |
-0.48 |
1.73 |
79.77 |
-0.31 |
2.07 |
15.72 |
| |
|
|
|
|
|
|
|
| B23 |
95.31 |
-0.47 |
1.49 |
85.67 |
-0.44 |
1.74 |
|
| |
95.55 |
-0.49 |
1.6 |
86.87 |
-0.44 |
1.7 |
|
| |
95 |
-0.51 |
1.08 |
89.36 |
-0.27 |
1.72 |
|
| |
95.26 |
-0.43 |
1.46 |
89.04 |
-0.52 |
1.63 |
|
| |
95.07 |
-0.38 |
1.32 |
87.81 |
-0.31 |
1.57 |
|
| Average |
95.24 |
-0.46 |
1.39 |
87.75 |
-0.40 |
1.67 |
7.49 |
| |
|
|
|
|
|
|
|
| B31 |
95.14 |
-0.49 |
1.6 |
75.8 |
-0.07 |
1.78 |
|
| |
95.36 |
-0.56 |
1.9 |
79.6 |
-0.2 |
1.63 |
|
| |
95.32 |
-0.54 |
1.67 |
79.05 |
-0.3 |
1.96 |
|
| |
|
|
|
|
|
|
|
| |
L |
A |
b |
L |
a |
b |
delta E |
| |
95.15 |
-0.45 |
1.63 |
75.16 |
-0.06 |
1.75 |
|
| |
95.28 |
-0.57 |
1.63 |
77.26 |
-0.46 |
1.84 |
|
| Average |
95.25 |
-0.52 |
1.69 |
77.37 |
-0.22 |
1.79 |
17.88 |
| |
|
|
|
|
|
|
|
| B32 |
95.04 |
-0.31 |
1.74 |
77.73 |
-0.21 |
2.25 |
|
| |
95.13 |
-0.42 |
1.83 |
78.92 |
-0.35 |
2.35 |
|
| |
94.85 |
-0.41 |
1.57 |
78.16 |
-0.18 |
2.18 |
|
| |
94.87 |
-0.29 |
1.55 |
78.59 |
-0.15 |
2.05 |
|
| |
94.84 |
-0.29 |
1.52 |
75.9 |
-0.31 |
1.93 |
|
| Average |
94.95 |
-0.34 |
1.64 |
77.86 |
-0.24 |
2.15 |
17.09 |
| |
|
|
|
|
|
|
|
| B33 |
95.14 |
-0.32 |
1.94 |
81.2 |
-0.04 |
1.79 |
|
| |
95.14 |
-0.38 |
1.88 |
82.73 |
-0.21 |
2.07 |
|
| |
95.17 |
-0.33 |
1.92 |
82.8 |
-0.27 |
2.1 |
|
| |
94.96 |
-0.33 |
1.75 |
81.99 |
-0.14 |
2.35 |
|
| |
94.98 |
-0.37 |
1.74 |
83.63 |
-0.01 |
2.23 |
|
| Average |
95.08 |
-0.35 |
1.85 |
82.47 |
-0.13 |
2.11 |
12.61 |
Table 7 - Carbon black contamination - alkyd paints - drying time 1 month
| |
INITIAL before contamination |
Surface washing with water |
|
| L |
A |
b |
L |
a |
b |
delta E |
| |
|
|
|
|
|
|
|
| PaintC-REF |
94.73 |
-0.33 |
1.75 |
76.68 |
-0.16 |
1.09 |
|
| |
95.01 |
-0.45 |
1.85 |
79.68 |
-0.16 |
0.98 |
|
| |
94.86 |
-0.35 |
1.78 |
76.9 |
0.12 |
1.38 |
|
| |
94.8 |
-0.32 |
1.59 |
75.01 |
-0.48 |
1.29 |
|
| |
95.01 |
-0.4 |
1.67 |
78.19 |
0.12 |
1.28 |
|
| Average |
94.88 |
-0.37 |
1.73 |
77.29 |
-0.11 |
1.20 |
17.60 |
| |
|
|
|
|
|
|
|
| Paint C21 |
95.17 |
-0.55 |
1.17 |
83.98 |
-0.34 |
0.94 |
|
| |
94.98 |
-0.36 |
1.32 |
84.55 |
0.07 |
0.97 |
|
| |
95.37 |
-0.39 |
1.35 |
84.27 |
-0.21 |
0.96 |
|
| |
95.04 |
-0.37 |
1.15 |
85.54 |
-0.1 |
1.05 |
|
| |
95.13 |
-0.35 |
1.23 |
84.73 |
-0.16 |
1.05 |
|
| Average |
95.14 |
-0.40 |
1.24 |
84.61 |
-0.15 |
0.99 |
10.53 |
[0058] From the results above, in tables 4-7, it can be clearly seen the yellowing effect
of the coating is reduced for paint formulations comprising Bindzil as indicated by
the b values prior to contamination compared to paints A and B (references). Also,
it can be noted the value of b after surface washing with water is maintained at a
lower level than paints without Bindzil and siccative which indicates acceptable b
values are obtained also after washing with water. Further, the dirt pick-up, measured
as the total colour difference, delta E is dramatically reduced, and hence the dirt
pick-up resistance improved, for the samples containing silanized colloidal silica
relative to formulation B and in some cases reach the same level as the siccative
containing formulation A. This is true for both types of dirt; hydrophilic iron oxide
dirt and hydrophobic carbon black dirt.
Vapour water permeability
[0059] The water vapour permeability was determined according to ISO 7783-1 (Determination
of water vapour transmission rate - part 1: Dish method for free films). The paints
were applied on a Teflon sheet. The dry film thickness was about 70 µm. The permeability
measurements have been carried out on seven disks for each paint after 14 days of
drying at room temperature The water-vapour transmission coefficient and vapour water
permeability have been calculated from the rate of change in mass of the dish assembly
according to the formula detailed in the ISO standard and are presented in Table 8
below.
Table 8 - Vapour water transmission
| |
Vapor water transmission coefficient (g/m2.d) |
|
Vapor water permeability (mole/m.s.Pa) |
|
| |
average |
std |
average |
Std |
| Paint A - REF |
70.18 |
2.28 |
4.50E-08 |
1.73E-09 |
| Paint B - REF |
121.74 |
11.78 |
7.47E-08 |
7.22E-09 |
| Paint B21 |
136.08 |
7.28 |
7.71E-08 |
4.13E-09 |
| Paint B22 |
190.83 |
10.99 |
1.15E-07 |
6.87E-09 |
| Paint B23 |
214.33 |
20.64 |
1.21E-07 |
9.16E-09 |
| Paint B31 |
104.23 |
5.13 |
5.66E-08 |
2.79E-09 |
| Paint B32 |
105.7 |
5.91 |
6.24E-08 |
3.49E-09 |
| Paint B33 |
103.07 |
6.69 |
5.87E-08 |
4.89E-09 |
| Paint C - REF |
65.41 |
5.53 |
3.89E-08 |
3.92E-09 |
| Paint C21 |
120.54 |
17.10 |
6.88E-08 |
9.03E-09 |
[0060] It can be clearly seen from all samples that the present invention outperform the
siccative-containing samples (references A and C) with respect to vapour water transmission.
Drying time
[0061] The drying time was measured according to ASTM 5896. A 120 µm (humid thickness) film
was applied on glass for the drying time determinations.. It describes a test method
for measuring times of drying or curing during film formation of organic coatings
using mechanical recorders. The mechanical recorders give valuable results for paints
that dry without skin formation at the paint surface. The considered time as drying
time is the one for which the needle of the recorder doesn't mark the paint film surface
anymore it is related to the total closing of the films. It has to be noted that a
permanent trace (very slightly) remains on the paint surface in all cases even when
the siccative agent is present The drying time recording has been conducted in triplicate,
they are presented in Table 9.
[0062] The following results showed that drying time is essentially maintained even in the
absence of a metallic drier. The addition of silanized silica in many cases reduced
the drying time relative to paint B and the Bindzil CC401 containing samples had almost
as short drying time as the siccative containing formulation, paint A.
Table 9 - Drying time
| |
Drying time (min) |
Average |
Std |
| PaintA-REF |
14.1 |
11.5 |
19 |
14.9 |
3.8 |
| Paint B -REF |
19.2 |
16.1 |
23.1 |
19.5 |
3.5 |
| Paint Ba* |
25.5 |
24.8 |
21.1 |
23.8 |
2.4 |
| Paint BB* |
23.4 |
26.3 |
24 |
24.6 |
1.5 |
| Paint B21 |
20.6 |
17.4 |
24.3 |
20.8 |
3.5 |
| Paint B22 |
20.3 |
18.5 |
23.8 |
20.9 |
2.7 |
| Paint B23 |
17.9 |
16.8 |
22 |
18.9 |
2.7 |
| Paint B31 |
14.9 |
18.3 |
12.4 |
15.2 |
3. 0 |
| Paint B32 |
17.7 |
18 |
13.8 |
16.5 |
2.3 |
| Paint B33 |
16.6 |
17.7 |
13.5 |
15.9 |
2.2 |
| Paint B1 |
36 |
36.3 |
29.6 |
34.0 |
38 |
| Paint B4 |
30.4 |
39 |
35.7 |
35.0 |
4.3 |
| Paint C -REF |
17 |
15 |
16 |
16.0 |
1.0 |
| Paint C21 |
28 |
25 |
21 |
24.7 |
3.5 |
*Ba has same dry content as B21
*BB has same dry content as B22
std: standard deviation |
Hardness tests
[0063] The hardness of the formulations was tested according to EN ISO 1522. The paints
were applied on tin plated steel (150 µm humid thickness). The results below indicate
the hardness in Persoz hardness (in seconds) after 1, 7, and 27 days respectively.
The Persoz hardness of the different paints listed in Table 10 have been determined
at 20°C and 50% relative humidity and each value is a mean of 5 measured values. It
can be noted the hardness is essentially maintained or improved in view of the siccative-containing
sample.
Table 10 - Persoz Hardness(s)
| |
1d |
|
7d |
|
27d |
|
| |
Average |
Std |
Average |
std |
Average |
std |
| Paint A - REF |
39 |
1 |
58 |
1 |
62 |
2 |
| Paint B - REF |
23 |
0 |
46 |
1 |
52 |
1 |
| Paint B1 |
22 |
0 |
46 |
1 |
53 |
1 |
| Paint B21 |
26 |
1 |
51 |
1 |
58 |
1 |
| Paint B22 |
30 |
1 |
62 |
0 |
71 |
0 |
| Paint B23 |
33 |
1 |
67 |
1 |
77 |
1 |
| Paint B31 |
30 |
1 |
53 |
1 |
61 |
1 |
| Paint B32 |
33 |
1 |
59 |
1 |
66 |
1 |
| Paint B33 |
37 |
1 |
67 |
1 |
75 |
1 |
| Paint B4 |
25 |
0 |
50 |
1 |
55 |
0 |
| Paint C - REF |
17 |
0 |
21 |
1 |
48 |
1 |
| Paint C21 |
21 |
1 |
30 |
1 |
64 |
2 |
1. Beschichtungszusammensetzung umfassend
a) silanisierte kolloidale Silicapartikel mit einem durchschnittlichen Partikeldurchmesser
von 2 bis 150 nm und einem Gewichtsverhältnis von Silan zu Silica von 0,05 bis 0,4
b) ein Alkyd enthaltendes Bindemittel
c) eine Trägerflüssigkeit, ausgewählt aus Wasser und/oder einem organischen Lösungsmittel,
wobei der Kobaltgehalt eines kobaltbasierten Trockners in der Zusammensetzung weniger
als 200 ppm, basierend auf dem Gewicht des Alkyd enthaltenden Bindemittels oder dem
Gesamtgewicht des Bindemittels, beträgt.
2. Zusammensetzung nach Anspruch 1, wobei die Zusammensetzung Kobalt in einer Menge von
weniger als 100 ppm, basierend auf dem Gewicht des Alkyd enthaltenden Bindemittels
oder dem Gesamtgewicht des Bindemittels, enthält.
3. Zusammensetzung nach Anspruch 1 oder 2, wobei kein Kobalttrockner in der Beschichtungszusammensetzung
vorhanden ist.
4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei die kolloidalen Silicapartikel
eine Größe von etwa 6 bis etwa 12 nm haben.
5. Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei das Gewichtsverhältnis der
silanisierten kolloidalen Silicapartikel zu dem Alkyd enthaltenden Bindemittel oder
der Gesamtmenge an Bindemittel von etwa 0,05 bis etwa 2 reicht.
6. Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei die Zusammensetzung eine wässrige
Dispersion ist.
7. Zusammensetzung nach einem der Ansprüche 1 bis 6, wobei die silanisierten kolloidalen
Silicapartikel in der Zusammensetzung in einer Menge von etwa 2 bis etwa 25 Gew.%,
basierend auf dem Trockengewicht oder dem Trägerflüssigkeit freien Gewicht der Zusammensetzung,
vorhanden sind.
8. Verfahren zur Herstellung einer Beschichtungszusammensetzung umfassend das Mischen
a) silanisierter kolloidaler Silicapartikel mit einem durchschnittlichen Partikeldurchmesser
von 2 bis 150 nm und einem Gewichtsverhältnis von Silan zu Silica von 0,05 bis 0,4;
und
b) eines Alkyd enthaltenden Bindemittels; und
c) einer Trägerflüssigkeit, ausgewählt aus Wasser und/oder einem organischen Lösungsmittel,
wobei der Metallgehalt eines der Zusammensetzung hinzugefügten Kobalttrockners weniger
als 200 ppm, basierend auf dem Gewicht des Alkyd enthaltenden Bindemittels oder dem
Gesamtgewicht des Bindemittels in der Beschichtungszusammensetzung, beträgt.
9. Verfahren nach Anspruch 8, wobei der Beschichtungszusammensetzung kein kobaltbasierter
Trockner hinzugesetzt ist.
10. Verfahren nach Anspruch 8 oder 9, wobei die silanisierten kolloidalen Silicapartikel
und das Alkyd enthaltende Bindemittel oder die Gesamtmenge des Bindemittels in einem
Gewichtsverhältnis von silanisiertem Silica zu Bindemittel von etwa 0,05 bis etwa
2 hinzugefügt werden.
11. Verfahren nach einem der Ansprüche 8 bis 10, wobei das Alkyd enthaltende Bindemittel
aus epoxidbasierten oder polyurethanbasierten Alkyden ausgewählt ist.
12. Verwendung einer Beschichtungszusammensetzung nach einem der Ansprüche 1 bis 7 zum
Beschichten eines Substrates.
13. Beschichtungszusammensetzung, erhältlich aus dem Verfahren, wie in einem der Ansprüche
8 bis 11 definiert.